Method of making black and gray vat dyes and the products thereof



Patented Mar. 8, 1932 Ares re NT ori ice i -A.RNGLI SHEPHERDSON ANDSIDNEY THORIJLEY, OF BLACKLEY, IflANGI-IESTER,

V sulphuric" acid.

' not obtained to alkaline j and the subsequent hy ENGLAND, ASSIGNOCHESTER, ENGLAND N0 Drawing. Application fi eeaug'ust 22, 1927,

In a co-pending application Serial N 0-. 193,378 of Sidney Th'ornley,filed May 21, 1927, there is described the productioniofnew vatdyestuffs by treating the dyesobtained vby alkaline fusion of benzanthrone sulphonlc acidwithhydroxylamine in the presence of We have nowfound that bluish-gray to violet and black dyes may e obtained from.benzanthrone sulphonrc acids, that 1s sulphonated benzanthrone bodiesincluding inthis latter term not of benzanthrone itsel merely sulphonicacids f, but also the sul-phoones, halogenated ben. by treating themwith subjecting theprodfusion. If desired, the sulphonation of thebenzanthrone body droxyla'mine treatment may be carried outwithoutisolation of the sulphonated' benzanthrone, thus effecting an economy bya reduced consumption of sulnatedmethyl benzanthr zanthrones and thehlre, nydroxylam'ine and then phuric' acid. 1

" alcoholic potash or i or caustic potash.

usual organic solvents.

' good methods of 40 sulphcnic acid are di sulphuric acid 66 :tion'of'?parts The dyestuffs are applied to the fibre from a vat, as is usualwith'vat dyestuffs.

The alkaline "fusion can be effected with Y with molten caustic soda Thenew dyestufls p ent invention are soluble in concentrated sulphuric acidwith ared-violet'to olive-green coloration, are appreciably soluble innitrobenzene and anilin, but are insoluble in other e hydrosulphite givea reddish-violet to blu ll dyeu in bluishvat from' which cotton isviolet to bluish gray or black shades.

The following examples will illustrate proceeding according to ourWithout limiting ourinvention parts of benzanthrone ssolved in 280 partsof Be. by stirring. 17.5' parts or" ferrous sulphate crystals are'added,followed after cooling by the gradual 'addi-, hydroxylaminehydrochloride.

invention,

Example [.'16.8

The. mixture is heated' with stirring to 150 C. and maintained at 150 C.for 2 hours,after which it is cooled of ice and water.

The mixtureis now stirred Serial No. 214,786, and in Great BritainAugust 24,

roduced by the pres- These new-dyestufis "tained' at 150 C 7 1t iscooled and p and poured into 1120' parts RS TO BRITISH DYIESTUFFSCORPORATION LIMITED, OF IVLAN- for several hours and filtered, theresidue be mg washed with 20 percent salt solution and dried. Theintermediate product thus' obtained is, in the form reddish-brownpowder. It dissolves in concentrated sulphuric acid to ayellow-orangesolution of the sulphate which exhibits-a green fluorescence. In dilutesulphuric acid it is soluble to a yellowbecomes reddish brown on theaddition of alkali. I I

10 partsof the productar to 100 parts of at 180 C. The tempera ture israduall L s y raised L0 210 d I uring which considerable frothing andevolution of ammonia. occursi The mixture is now kept at 240 Cifor 1hour, after which it is cooled and extracted with 2000 parts of water.The whole'is heated up, air blown throughand filtered. the residue beingwashed with dilute caustic soda. is now boiled-up with dilutehydrochloric acid, filtered, and he residue washed --withwater, drainedand dried The product dyes cotton bluish-gray to bluish black "shades.

Example [I parts of benzanthrone are stirred at 98-100 C. with 210 partsof omplete sulphona+ this is indicated by C0111- plete solubility of atest portion in water." The mixture is now diluted with 10 parts ofwater and 580 parts of sul and stirred. crystals are ad lowed by thegradual" addition of 20 hydroxylamine hydrochloride.

is heated withstirring'to 150 tion has occurred 7 ferrous sulphate ded,the wh of its sodium salt, a i

orange solution which e gradually added stirred molten caustic potashole cooled, folparts dried. The product dyes cotton ,anthraquinone, beused, a very similar huric acid (96 per cent) owed by 12 parts of waterfrom a burette,

for 1 hour, after which it is cooled and extracted with 2000 parts ofwater. The whole is heated up, air blown through to oxidize, andfiltered, the residue being washed with dilute caustic soda. It is nowboiled up with dilute hydrochloric acid, filtered, and the residuewashed with water, drained and bluish-gray to bluish-black shades.

If in place of the 30 parts of benzanthrone, 31.8 parts ofmethylbenzanthrone, melting point 197-199 0., prepared from 2-methyldyeis obtained.

Instead of hydroxylamine a solution of hydroxylamine as obtained by theelectrolytic reduction of nitric acid may be employed.

Emample HL-23 parts of Bz-l-chlorobenzanthrone, having the formula arestirred at 15-20 7 per cent oleum until the solubility of a test ortionin water indicates that complete sulphonation has occurred. 152 parts ofsulare then added folthe whole being cooled in a water-bath. Then 24parts of well ground ferrous sulphate crystals are added followed by thegradualaddition of 13.2 parts of hydroxylamine hydrochloride. Themixture is now heated to, and maintained at 145-150 C. for 2 hours.

mixture is poured into 800 parts of ice and 800 parts of water, stirred,200 parts of salt added, restirred, and filtered. The residue is washedacid-free with 20 per cent salt solution and dried. (During the washingthe 7 colour changes from yellow-brown to chocostirring at raised to 230late). Yleld 60 parts of powdered caustic potash, an parts of absolutealcohol are 150-155 C. for half-an-hour. The temperature is now raisedto 170 C. distilling off at the same time 10 ccs.-of cohol. 1 8.2 partsof the 60.5 parts ofthe intermediate are now added the temperature ismaintained at 170175 C. for 1 hour, C. in half an hour, and maintamed at230240 C. for 2 hours. The melt after cooling is extracted with water,boiled, and oxidized by passing through it a stream =60.5 partscontaining salt.

v of air. It is then filtered and the residue washed alkali-free withhot water, an dried. Yield==6.0 parts of pure dyestufi I representing atotal yield of 19.9 parts from the 23 parts of 3-chloro-benzanthrone.

C. with 240 parts of 7 0 After cooling the reaction al- I sulphonatedmethylbenzanthrone and sodium hydrosulphite it cotton caustic soda givesa blue coloured vat which dyes after oxidation a violet shade.

Ewample IV.1 part of paste (10 per cent) made from dyestuif preparedaccor ing to any of the preceding examples is duced by stirring with 5parts of water, 8.5 parts of caustic soda solution 76 Tw. and 1.5 partsof sodium hydrosulphite and adding this mixture to 1250 parts of water a60 C. To the vat thus prepared 50 parts of cotton are added and workedat 60 (Lfor half an hour. The cotton is rinsed, the dye oxidized byexposure to air, and the material then acidified, rinsed, soaped anddried.

What we claim and desire to secure Letters Patent is 1. The process forthe manufacture of dyes, comprising the condensation of a phonatedbenzanthrone compound of the class consisting'of sulphonatedbenzanthrone, sulphonated alkyl benzanthrone and sulphonated halogenatedbenzanthrone, with hyforlthe manufacture of d es, comprising thecondensation of a sulp onated benzanthronc compound of the classconsisting ,of sulphonatel methyl benzanthrone and sulphonatedchlorobenzanthrone, with hydroxylamine, followed by alkaline fusion ofthe product so obtained using alcoholic. potash. 3. As new products,stufis obtainable by the alkaline fusion 0 the condensation product of asulphonated benzanthrone compound of the class consisting of sulphonatedbenzanthrone, sulphonated alkyl benzanthrone and sulphonated halogenatedbenzauthrone, with hydroxylamine, the said dyestuffs being soluble inconcentrated sulphuric acid with a redviolet to olive-green coloration,appreciably soluble in nitrobenzene and anilin, but inother usualorganic solvents, the said dyestuffs yielding a reddish-violet to 2. Thea process the group of vat dyedyed in 0 shades. heated with 4. As newproducts, the members of the group of vat dyestufls obtainable by thealkaline fusion of the condensation product of a sulphonatedbenzanthrone compound of the class consisting of sulphonatedbenzanthrone,

and sulphonated chlorobenzanthrone, with hydroxylamine, said members ofsaid group being soluble in concentrated sulphuric acid with ared-violet coloration, appreciably soluble in nitrobenzene and anilinbut insoluble in other usual organic solvents, said members yielding areddish-violet hydrosulphite vat from which cotton is dyed in bluishgrayto black shades. 5. As a new product, a member of the sul- . classconsisting of benzanthrone,

group'of vat dyestufi's obtainable by the alkaline fusion of thecondensation product of a sulphonated benzanthrone trated sulphuric acidwith coloration, appreciably soluble in nitrobenzone and anilinbutinsoluble in other usual organic solvents, said member yielding a red-'dish-violet hydrosulphite vat from which cotton is dyedin bluish-gray toblack shades;

6. In the manufacture of dyes from sulphonated benzanthrone compounds ofthe zanthrone and halogenated-benzanthrone, the process which comprisessulphonating such a benzanthrone compound by reacting the same with asulphonating agent,condensing the sulphonated' product thus producedwith hydroxylamine and'then subjecting the' I condensation product to analkaline fusion 7 and recovering the said dye.

7. The process of claim 6'in which the sul-' phonating agent is oleum.

8. In the manufactureof dyes from.sulphonated benzanthrone compounds ofthe class consisting of benzanthrone, alkyl-benzanthrone andhalogenated-benz'anthrone,--

the process which comprisessulphonating ben- Zanthrone by reactingthesame with a sul-* phonating agent, condensing the sulphonated productthus produced with not to an alkaline fusion and recovering the saiddye. g I q 9. Inthe manufacture of dyes fromsul phonatedbenzanthronecompounds of the class consisting of benzanthrone,alkyl-ben-' Zanthrone and halogenated benzanthrone;"

the process which comprises sulphonating ,methyl-benzanthrone byreacting the samewith a sulphonating agent, condensing the sulphonatedproduct thus hydroxylamine and then subjectingthe con densationproducttoan alkaline fusion and recovering the said dye.

10. In the manufacture ofv dyes from sulphonated benzanthrone compoundsof the class consisting of benzanthrone, alkyl-ben-' zanthrone andhalogenated-benzanthrone,the

process which comprises sulphonating chloro benzanthrone sulphonatingagent, condensing the sulphon-" by reacting the same with a ated productthus produced with hydroxyl amine and then subjecting the condensationproduct to an alkaline fusion and recovering the. said Y ll. In themanufacture of dyes from sul phonated benz'anthrone compounds of theclass consisting of benzanthrone, methyl-hem zanthrone andchlorobenzanthrone, the proc- Y ess whichcomprises sulphonating such abenby. reacting the same I with a sulphonating agent, condensing in thedye.

zanthrone compound presence of sulphuric acid thesulphonated compoundthus produced'with a hydr'oxylamwith hydroxyL amine, said member beingsoluble in concena dull red-violet alkyl-benhydroxlamine' and thensubjectingthe condensation prod-"- produced with a f iiie material ofthe class consisting of by. droz c'ylamine and salts of hydrox lamine,and then su-bj-ecting the condensation product to an alkaline fusion andrecovering the said dye 4 12.- The process of claim hydrox'ylaminecompound is hydroxylamine hydrochloride;

13. In the manufacture of dyes from $111- phonated benz'anthronecompounds of the class consisting of benzanthrone, methyl-ben- 11 inwhich the zanthrone and chlorobenzanthrone, the procconcentratedsulphuric acid with ared-violet coloration and appreciably soluble innitrobenzen'e and aniline but insolublein other organic solvents, saidmember yielding a reddish-violet 'hydrosulphite ,vat from whiclcotton isdyed in bluish-gray shades.

'15. A's a new product, afmemb'er of the group ofvat dyestuffsobtainable by the alkal ne fusion of the condensation product'ofsulphonated chlorobenzanthrone ,with hy H 'droxylamine, said memberbeing soluble in concentrated sulphuric acid With a red-violetcoloration; being appreciably soluble innitrobenzene and anilinebutbeinginsoluble inother organic solvents. L

l6; In the-man'ufacture ofdyes, the process which comprises dissolvingasulphonated benzanthrone compound of the class consisting ofb'enzanthrone sulphonic acid, sulphonated Q-methyLbenzanthrdne andsulphonjated BZ-l-chlorobenzanthrone, in. sulp'huric acid of 66 B.strength, adding fer- 5 rous sulphate crystals to. the solution thusobtained,*cooling the solution,gradually add ing hydrox-ylaniine'hydrochlorid', heating the 5 mixture thus obtained to effect reaction'beg tween saidsulphonated benzanthrone com- 'po1'1nd and thehydroxy-lamine compound, pouring the reaction product into a mixture oficeand water, isolating, purifying and drying the reaction product thusobtained, fusing the dried'reaction product. with caustic potash,cooling themelt and extracting with water, heating, the solution thusobtained andioxidizing by passing air through ,said solu'tion,isolating; purifying and drying'the precipitated dyestufi thus obtained.

which comprises reactingbenzanthrone With 7 per cent oleum toproduce aben'zanthrone i 17. n the nanufactureoffdyes, the process sulphonicacid, issolving said benzanthrone, i sulphonic acid in sulphuric acid of66, B.

, strength, adding ferrous sulphate crystals i. to the solution thusobtained, cooling the solution, gradually adding hydroxylamine hy-,

, drochlorid, heating the mixture thus obtained to effect reactionbetween said benzanthrone compound and said hydroxylamine compound,pouring the reaction product into a mixture ofice and water, isolating,purifying and drying the reaction product thus obtained, fusing thedried reaction product with 1 caustic potash, cooling the melt andextract- 'ing with Water, heating the solution thus oh- 1 1 tained andoxidizing by passing air through said solution, isolating, purifying anddrying the precipitated dyestuif thus obtained.

18. In the manufacture of dyes, the process which comprises reactingZ-methyl-beni zanthrone with 7 per cent ole'um to produce aQ-methyl-benzanthrone sulphonic acid, dissolving saicl2-inethyl-benzanthrone sul-r V phonic acid in sulphuric acid 0 6 B.

strength, addingferrous sulphate crystals 1 I to the solution thusobtained, cooling the solution, gradually adding hydroxylaminehydrochlorid, heating theinixture thus obtained to effect reactionbetween said benzanthrone 7 compound and said 'hydroxylamine com-.

pound, pouring the reaction product into a mixture of ice and Water,isolating, purifying anddrying the reaction product thus 0b-. 1

'tained, fusing the dried reaction product with caustic potash, coolingthe melt and extracting with Water,heating the solution thus:

obtained and oxidizing. by passing air through said solution,-isolating,purifying, i

and drying the precipitated dyestuif thus obtained.

4 19. In the manufacture of dyes, the proc ess which comprises reactingBz-l-chlorobenzanthrone with 7 per cent oleum to produce aBz-l-chlorobenz anthrone sulphonic acid, dissolving saidBz-l-chlorobenzanthrone sul-l i,

phonic acid in sulphuric acid of 66 B. strength, adding ferrous sulphatecrystals to the solution thus obtained, coolingthe solu-- ''tion,gradually addinghydroxylarninehydro- -i v chlorid, heating the mixturethus obtained to eifectreactionbetweensaidbenzanthronecom- I poundandsaid hydroxylamine compound, pouring the reaction'product intoamixture of ice andwater, isolating, purifying and drying the reactionproduct thus obtained,

fusing the dried reaction product withcaustic potash, cooling the meltand extracting with water, heating the solution thus obtained "andoxidizing by passing air through said solution, isolating, purifying anddrying the precipitated dy'estuffthus obtained. 7

= Intestimony whereofweafiix our signa- I tures. I c -lABNOLDSHEPHERDSON. I I

- SIDNEY ,THORNLEY.) j

CERTIFICATE OF CORRECTION.

Patent No. 1,848, 228. Granted March 8, 1932, to

ARNOLD SHEPHERDSON ET AL.

It is hereby certified that error appears in the printed specificationof the above numbered patent requiring Correction as follows: Page 3,line 79, claim 13, for the Word "as" read a; and that the said LettersPatent should be read with this eerreetien therein that the same mayconform to the record of the case in the ?atent (lifiee.

Signed and sealed this 26th day of April, A. D. 1932.

' M. J. Moore, (Seal) Acting Commissioner of Patents.

